Waterinsoluble azodyestuffs derived from benzocarbazoles



Patented Jan. 21, 1936 UNITED STATES PTENT ()FFIQE WATERINSOLUBLE AZODYESTUFFS DE- RIVED FRO BENZOCARBAZOLES Wilhelm Neelmeier, Leverkusen-Vieisdorf, and Heinrich Morschel, Cologne-Deutz, Germany, assignors to Genera! Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing.

Serial No. 656,624. 1932 10 Claims.

wherein R stands for a tetramethine chain linked to two vicinal carbon atoms of the benzene nucleus R, R stands for a non-sulfonated and non-carboxylated aromatic radical, such as a radical of the benzene, naphthalene and carbazole series, and R' stands for the radical of a non-sulfonated and non-carboxylated diazotized component suitable for producing azodyestuffs; as substituents which may occur in the nuclei R and R' there may be mentioned by way of example, alkyl, alkoxy, halogen and the nitro group.

Our new waterinsoluble dyestufis are obtainable by coupling in substance or on a. substratum a diazotized non-sulfonated and non-carboxylated amine suitable for producing azodyestuffs with a 5, 6-, 6, 7-, or 7, 8- benzo-Z-hydroxycarbazole-3-carboxylic acid arylamide. The shades when produced on the fibre, according to the usual method of producing ice colors, are distinguished by good fastness properties.

The coupling components used in our invention have been described and claimed in the application for Letters Patent Serial No. 656,622, filed February 13, 1933 and entitled New hydroxybenzocarbazole compounds, one of us being a co-inventor in said application. They are obtainable by carbonating 2-hydroxybenzocarbazole and condensing the 2-hydro'xybenzocarbazole-3carboxylic acid with non-sulfonated and non-car boxylated aromatic amines to the corresponding arylamides.

The invention is illustrated by the following examples, without being limited thereto:

Example 1.20 grams of well boiled and dried cotton yarn are impregnated for half an hour in one liter of an aqueous solution containing 3 grams of 2-hydroxy-5,6-benzocarbazole-3-carboxylic acid-p-chloroanilide, 10 cos. of aqueous Application February 13, 1933, In Germany February 18,

caustic soda of 34 B. strength and 10' cos. of Turkey red oil of 50% strength, well squeezed and, without drying, introduced for about half an hour into a diazo solution of one liter, prepared in the usual manner by diazotizing 2 grams of 4-chloro- 2-toluidine and neutralizing the mineral acid by the addition of sodium acetate. The cotton is rinsed, soaped in a boiling bath and dried. A yellowish-brown of good tastness properties is thus obtained. The dyestufi probably has the following formula:

Example 2.-20 grams of well boiled and dried cotton yarn are impregnated for half an hour in one liter of an aqueo'us solution containing 1.2 grams of 2hydroxy-7,8benzocarbazole-3 carboxylic acid-p-anisidide, 10 cos of aqueous caustic soda of 34 B., and 10 ccs of Turkey red oil of 50% strength, well squeezed and, without drying, introduced for about half an hour into a diazo solution of one liter, prepared in theusual. manner by diazotizing 2 grams of 2-chloroaniline and neutralizing the mineral acid by the addition of sodium acetate. The cotton is rinsed, soaped in a boiling bath and dried. A yellowishbrown of excellent fastness properties is thus obtained.

40 The dyestufi corresponds to the probable formula In the following table there are given some further combinations and their shades, obtain able in an analogous manner:

Diazctization com- I Coupling component pollen: Shade tbydroxyd, S-benzocarbazole- B-chloroaniline. Khakibrownl ilcarboxylic acid-pxrbloroani ide Do 2-chloroanl]ine Yellowlshbrown. Do 4nitro-2-anisldine Brown. Do 'l-arninonaphtha- Do.

lene. 2bydroxy-5.G-benzocarbazole- -chloro l-tolul- Yellowish- Zlcarborylic acid-m-chlorome. brown. 8Dllld6 Do. w 2-chloroanlllne.. Do.

Do v v a .S-chloro-Z-Lolul- Brown.

dine. Do or 4-nitro 2anisidine. R e d d i s 11 brown Lhydroxy-b. tibenzocarbazole- Scbloroaniline Khakibrown.

K-carboxylic acid-o-toluidide.

D V 7 a a v o V 2-chloroaniline Brown Do l. 4-chloro 2-tolui Yellowishdine. brownl D0 finitro-Z-auisidinm R e d d i s b brown. 2 hydroxy-5, 6-benzocarba1ole- 2-chloroaniline Brown Iicarboxyllc acid-a napbthylamide Zhydroxy-Z 8*benz0carbazole- 4-chloro-2-t0lul Y 01 lo w i s h 3-mrboxylic acid-p-anisidide. brown.

2-hydroxy-7. 8-benzocarbazolo 3carboxylic ncid-o-rnel:byl-

De. 2, 5-dichloro-ani line.

Orange brown.

p-anisidide.

Do rn-amido nzo-tol- Reddish dark uene. brown. Do zrcblormihenzoyl- R e d d i s )1 aminoamethoxyaniline.

brown.

2-hydroxy-7.8-benzocarbatole (-Ditro2-anisidine Brown.

3-carboxylic acid 2 carbazoleamide.

2 hydroxy-7i B-benzocarbazole- Z-chloroanillne. l. Y e l l 0 w l s l:

Kcarboxylic acid-fl'naphthylbrown. amide.

2-hydroxy-7. 8-benzocarbazole- 2, S-dichloromnlliner 4-nitro2-anisldine.

i-chloroQ-anish 4-nitro2-toluldine z-arninonaphthalene Orange brown.

R e d d l s h brown.

Orange brown. Brown.

We claim:

1. Dyestufis of the formula:

wherein R stands for a tetramethlne chain linked to two vicinal carbon atoms of the benzene nucleus R, R" stands for a non-sulfonated and noncarboxylated radical of the aromatic series, and R' stands for the radical of a non-sulfonated and non-carboxylated diazotized component suitable for producing azodyestulfs, yielding, when produced on the fibre; various shadesof good fastness properties.

2. Dyestuffs of the formula:

wherein R" stands for a non-sulfonated and non-carboxylated radical of the benzene or naphthalene series, and R' stands for the radical of a non-sulfonated and non-carboxylatcd diazotlzed component suitable for producing azodyestuffs, yielding, when produced on the fibre, various shades of good fastness properties.

3. Dyestuffs of the formula:

wherein R" stands for a non-sulfonated and noncarboxylated radical of the benzene or naphthalene series, and R stands [or the radical of a nonsulfonated and non-carboxylated diazotized component suitable for producing azodyestuffs, yielding, when roduced on the fibre, various shades of good fastness properties.

4. The dyestufl of the formula:

yielding, when produced on the fibre, yellowishbrown shades of good fastness properties.

5. The dyestuff of the formula:

9. Fibre dyed with the dyestuff as claimed-in claim 4.

10. Fibre dyed with the dyestufi as claimed in claim 5.

WILHELM NEELMEIER. HEINRICH MORSCHEL. 

